1. Field of the Invention
This invention relates to amphiphilic compounds with at least, two hydrophilic and at least two hydrophobic groups based on di-, oligo-, or polyenes and also to a process for their preparation, and to their use as dispersants, emulsi-fiers, demulsifiers, as auxiliaries in ore mining, metal working, surface finishing, plastics production or processing, as auxiliaries for the application of crop protectants, as adjuvants in medical applications, as textile auxiliaries, as auxiliaries for the cleaning and washing of textiles, as auxiliaries for the cleaning of hard surfaces, and as auxiliaries for the cleaning and washing of skin and hair.
2. Description of the Related Art
A wide variety of anionic, cationic, nonionic, and zwitterionic compounds are known as amphiphilic substances. By far the most of these substances consist of a hydrophilic head group and at least one hydrophobic moiety.
With the amphiphilic substances there is a need, for ecological reasons, for example regarding the reduction in packaging and transportation expenditure, to achieve an increasingly greater effect per mass of substance employed. Since only little optimization can be achieved by mixing amphiphilic substances, novel amphiphilic substances with greater efficiencies are required. In particular, there is a need for substances having lower critical micelle concentrations and/or lower surface and interfacial tensions in order to significantly reduce the amount of active substance used.
Initial approaches to solving this problem by doubling part of the structure (hydrophilic head group, hydrophobic group) have already been disclosed. For example, it is known to prepare cationic surface-active compounds by addition of long-chain alkyl halides to permethylated alkylene diamines [see Zana, R., Benrraou, M., Rueff, R., Langmuir, 7 (1991), p. 1072; Zana, R., Talmon, Y., Nature, 362 (1993), p. 228; Alami, E., Beinert, G., Marie, P., Zana, R., Langmuir, 9 (1993), p. 1465].
Anionic surface-active compounds with at least two hydrophilic and at least two hydrophobic groups have to date been prepared only on the basis of diglycidyl ethers (cf. U.S. Pat. No. 5,160,450, JP 01 304 033, JP 4 124 165). However, diglycidyl ethers are regarded as toxicologically objectionable and are rather expensive. Furthermore, epichlorohydrin is used for their preparation, which results in large amounts of residues so that said compounds are no longer in accord with the times both in ecotoxicological and economic aspects.
Therefore, it was an object of the present invention to prepare amphiphilic compounds which have at least two hydrophilic and at least two, hydrophobic groups, wherein the amphiphilic compounds have very high efficiencies, relative to the feed quantity, and, furthermore, can be prepared from raw materials which are technically readily available without producing large amounts of undesirable by-products.
According to the present invention, the problem is solved by providing amphiphilic compounds based on di-, oligo-, or polyenes.
The amphiphilic compounds of this invention are compounds which, when alkylene dienes are used, typically correspond to the general formulae I and II. The result is analogous for the reaction of a plurality of double bonds.
Formula I 
Formula I 
The invention therefore relates to amphiphilic compounds of the general formulae I and II or, on reaction of a plurality of double bonds, analogous structures.
Formula I 
Formula II 
where
R1 and R3, independently of one another, represent an unbranched or branched, saturated hydrocarbon radical or a partially fluorinated or perfluorinated hydrocarbon radical having 1 to 22, preferably 6 to 18, carbon atoms,
R2 is a spacer,
and X and Y, independently of one another, are substituents of the formula XV
xe2x80x94(C2H4O)xcex1(C3H6O)xcex2Hxe2x80x83xe2x80x83(XV)
xe2x80x83where
xcex1=0 to 50, preferably xcex1=0 to 15,
xcex2=0 to 60, preferably xcex2=0 to 10, and
xcex1+xcex2=1 to 100, preferably xcex1+xcex2=1 to 20,
xe2x80x83or of the formula XVI
xe2x80x94(C2H4O)xcex3(C3H6O)xcex4xe2x80x94FRxe2x80x83xe2x80x83(XVI)
xe2x80x83where
xcex3=0 to 20, preferably xcex3=0 to 8,
xcex4=0 to 20, preferably xcex4=0 to 12, and
xcex3+xcex4=0 to 40, preferably xcex3+xcex4=0 to 20, and
FR is a functional radical xe2x80x94CH2xe2x80x94COOM, xe2x80x94SO3M, xe2x80x94P(O)(OM)2, xe2x80x94C3H6xe2x80x94SO3M, or xe2x80x94Oxe2x80x94C(O)xe2x80x94C2H3(SO3M)xe2x80x94CO2Mxe2x80x2 with M, Mxe2x80x2 representing alkali, ammonium-, substituted ammonium-, or xc2xd alkaline earth metal ion,
xe2x80x83and where the alkoxide units are incorporated randomly or blockwise, and the sequence is arbitrary.
Examples of the substituents R1 and R3 include the radicals methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-henicosyl, n-docosyl, and branched-chain isomers thereof as well as their partially fluorinated or perfluorinated equivalents.
R2 is a spacer consisting of an unbranched or branched chain with 2 to 30 carbon atoms which comprises 0 to 10 oxygen, 0 to 10 nitrogen, and 0 to 3 sulfur atoms and which has 0 to 10 functional side groups, such as carbonyl, carboxyl, amino and/or acylamino groups.
The spacer R2 represents in particular
unbranched or branched alkylene chains as a body
xe2x80x94CaH2axe2x80x94xe2x80x83xe2x80x83(III)
where a=2 to 18, preferably a=2 to 6;
alicyclic compounds ofthe formula IV as a body
xe2x80x94CfH2f-cycloC6H10xe2x80x94CgH2gxe2x80x94xe2x80x83xe2x80x83(IV)
where each f and g, independently of one another, is equal to from 1 to 6;
xe2x80x83or of the formula V
-3(4),8(9)-di(methylene)-tricyclo[5.2.1.02.6]decane-xe2x80x83xe2x80x83(V)
optionally as a body, substituted aromatics of the formula VI
xe2x80x94ChH2hxe2x80x94C6R4xe2x80x94(CiH2ixe2x80x94C6R4)j1xe2x80x94Cj2H2j2xe2x80x94xe2x80x83xe2x80x83(VI)
xe2x80x83or of the formula VII
xe2x80x94ChH2hxe2x80x94C10R6xe2x80x94CjH2jxe2x80x94xe2x80x83xe2x80x83(VII)
where each h, j, j1, and j2, independently of one another, is equal to from 0 to 8, and i is equal to from 0 to 8, and each R in the formulae VI and VII, independently of one another, is equal to H or C1xe2x80x94 to C6-alkyl;
a chain with functional side groups, particularly carbonyl, carboxyl, amino and/or acylamino groups.
The spacer R2 furthermore comprises in each case from 0 to 10, preferably from 1 to 5, oxygen and/or nitrogen atoms and/or from 0 to 3 sulfur atoms.
Thus, R2 furthermore represents in particular
a compound of the formula VIII
xe2x80x94CkH2kxe2x80x94CxRyxe2x80x94Zxe2x80x94CxRyxe2x80x94C1H21xe2x80x94xe2x80x83xe2x80x83(VIII)
xe2x80x83where
each k and l, independently of one another, is equal to from 0 to 8, each R, independently of one another, is equal to H or C1xe2x80x94 to C6-alkyl, x is equal to 6 and y is equal to 4, or x is equal to 10 and y is equal to 6, or x is equal to 14 and y is equal to 8, and
Z=O, CO, NH, NR1, Nxe2x80x94C(O)R1, SO2 
xe2x80x83or of the formula IX
xe2x80x94CH2xe2x80x94CH(OCH2CH(OX)xe2x80x94R1)xe2x80x94CH2xe2x80x94 or an isomerxe2x80x83xe2x80x83(IX)
xe2x80x83or 2,2xe2x80x2-methylene-bis-(1,3-dioxolane-5-methylene)-, or acetals, particularly diacetals of dialdehydes and di-, oligo-, or polyols,
wherein R1 is a hydrocarbon radical having 1 to 22 carbon atoms;
a compound of the formula X
xe2x80x94CmH2mxe2x80x94(OCnH2n)pxe2x80x94CqH2qxe2x80x94xe2x80x83xe2x80x83(X)
where m=1 to 4, n=2 to 4, p=1 to 20, preferably p=1 to 4, and q=1 to 4, wherein mixed alkoxide units may also be present and if that is the case, the sequence of said alkoxide units is arbitrary;
a compound of the formula XI
xe2x80x94CrH2r(RNCsH2s)txe2x80x94CuH2uxe2x80x94xe2x80x83xe2x80x83(XI)
xe2x80x83or of the formula XII
xe2x80x94[CrH2r[RNxe2x80x94C(O)xe2x80x94NR]txe2x80x94CuH2u]wxe2x80x94xe2x80x83xe2x80x83(XII)
xe2x80x83or of the formula XIII
xe2x80x94[CrH2r[RNC(O)CvH2vC(O)NR]txe2x80x94CuH2u]wxe2x80x94xe2x80x83xe2x80x83(XIII)
xe2x80x83or of the formula XIV
xe2x80x94[CrH2r[RNC(O)CxRyC(O)NR]txe2x80x94CuH2u]wxe2x80x94xe2x80x83xe2x80x83(XIV)
xe2x80x83where
r=2 to 4, s=2 to 4, t=1 to 20, preferably t=1 to 4, u=2 to 4, v=0 to 12, w=1 to 6, x=6, and y=4, or x=10 and y=6, or x=14 and y=8,
and R, independently of one another, is equal to H or C1xe2x80x94 to C6-alkyl.
X and Y, independently gf one another, are substituents of the formula XV
xe2x80x94(C2H4O)xcex1(C3H6O)xcex2Hxe2x80x83xe2x80x83(XV)
where
xcex1=0 to 50, preferably xcex1=0 to 15,
xcex2=0 to 60, preferably xcex2=0 to 10,
xcex1+xcex2=1 to 100, preferably
xcex1+xcex2=1 to 20;
or substituents of the formula XVI
xe2x80x94(C2H4O)xcex3(C3H6O)xcex4xe2x80x94FRxe2x80x83xe2x80x83(XVI)
where
xcex3=0 to 20, preferably xcex3=0 to 8,
xcex4=0 to 20, preferably xcex3=0 to 12, and
xcex3+xcex4=0 to 40, preferably
xcex3+xcex4=0 to 20, and
FR represents a functional radical xe2x80x94CH2xe2x80x94COOM, xe2x80x94SO3M, xe2x80x94P(O)(OM)2, xe2x80x94C3H6xe2x80x94SO3M, or xe2x80x94C(O)xe2x80x94C2H3 (SO3M)xe2x80x94CO2Mxe2x80x2 with M, Mxe2x80x2 representing alkali, ammonium, substituted ammonium, or xc2xd alkaline earth metal,
and where the alkoxide units are incorporated randomly or blockwise and the sequence is arbitrary.
In each case the degree of alkoxylation is an average value which can be any desired value, even a non-integral one, within the specified limits.
A further object of the present invention is a process for preparing the amphiphilic compounds described hereinabove, wherein the preparation comprises two steps.
In each case there are obtained mixtures of said compounds because the opening of the epoxides formed during the reaction according to this invention takes place with selectivities of only 50 to 90%, preferably 70 to 80%, from the less substituted side.
The first step comprises the preparation of hydroxy ethers (X, Y=H, formula I or II and analogous structures) by reacting di- or oligoenes, which may be cyclic or acyclic, with organic hydroperoxides, ROOH, as oxidants and opening of the resultant oxirane ring by mono- or polyhydric alcohols in the presence of homogeneous or heterogeneous molybdenum compounds as a first catalyst component and boron trifluoride, as a stabilized complex, or of an alumina or 1,8-diaza-bicyclo-[5.4.0]-undec-7-ene or 1,4-diazabicyclo-[2.2.2]-octane as a second catalyst component and use of mono- or polyhydric alcohols as a nucleophile and simultaneously as a solvent, the use of other solvents not being precluded.
In a second step according to this invention the resultant di- or oligools are converted into nonionic surfactants with the aid of alkoxylating agents, or are converted, preceded by alkoxylation or directly, into anionic, amphiphilic compounds. This can be achieved for example by oxidizing the compounds referred to hereinabove with sulfur trioxide/inert gas, oleum, chlorosulfonic acid or sulfamic acid, with polyphosphoric acid, with a haloacetic acid or with oxygen in the presence of a TEMPO derivative (TEMPO derivatives are derivatives of 2,2xe2x80x2,6,6xe2x80x2-tetramethylpiperidine oxides), by reaction with a sultone, a taurine, or with maleic anhydride and sodium bisulfite and, in each case, by subsequent neutralization with aqueous alkali or alkaline earth metal hydroxides or aqueous ammonia or alkanol amines. Optionally, the products can be bleached in aqueous solution with hydrogen peroxide (0.1 to 2.0% based on solid).
Although the individual components of the reaction are known, it is surprising that they can be combined in a xe2x80x98one-pot processxe2x80x99 and that the xcex1-hydroxy ether is formed selectively in the reaction. The catalyst components do not adversely affect one another, and it can in fact be observed that BF3 enhances the activity of the molybdenum catalyst for the epoxidation.
Suitable epoxidation catalyst components for the process according to the invention are molybdenum compounds which are soluble in the reaction mixture, such as molybdenum acetylacetonate, MoO2(acac)2, or molybdenum hexacarbonyl, Mo(CO)6. Also suitable is molybdenum oxide on a catalyst carrier as a heterogeneous catalyst. Appropriate catalyst carriers are amorphous aluminosilicates or zeolites with high Lewis acidity. The molybdenum catalyst is employed in quantities of from 0.01 to 5 mol %, preferably 0.25 to 2 mol %, most preferably 0.5 to 1.0 mol %, based on the Cxe2x95x90C double bond to be oxidized.
According to the invention, it is possible to employ as a second catalyst component boron trifluoride or adducts, such as the etherate or the methanolate. Also suitable are alumina, Al2O3, and the basic compounds 1,8-diazabicyclo-[5.4.0]-undec-7-ene or 1,4-diazabicyclo-[2.2.2]-octane. These catalyst components are employed in quantities of from 0.01 to 5 mol %, preferably 0.25 to 2.0 mol %, most preferably 0.5 to 1.0 mol %, based on the Cxe2x95x90C double bond to be oxidized.
The olefinic substrates which can be employed are terminally and/or internally di- or polyunsaturated aliphatic, cyclic, or acyclic hydrocarbons or fatty acids and their esters. Expediently, the alcohol component in the fatty acid esters should be the same as the alcohol used in order that the transesterification which is likewise catalyzed does not yield undesirable product mixtures.
It is possible to employ for the process according to the invention mono- or polyhydric alcohols with primary, secondary, or tertiary hydroxyl groups and any desired chain length. If compounds of the formula II are to be prepared, only primary hydroxyl groups should be employed for the etherification in order to avoid undesirable product mixtures. The alcohol and the olefinic substrate may comprise further functional groups, such as ester groups, carbonyl carbons, amides, ethers, as long as said groups are unable to compete effectively as nucleophiles in the reaction.
Suitable oxidants for the process according to the invention include commercially available hydroperoxides, such as tert-butyl hydroperoxide; or cumene hydroperoxide. The oxidant is employed at a ratio of 1.0:1.3, based on the double bond equivalents to be oxidized.
The reaction in the process according to the invention can be carried out at temperatures starting at the melting point of the reaction mixture and ending at the boiling point of the reaction mixture. The reaction is furthermore preferably carried out under an inert gas atmosphere and with anhydrous reagents. For the reaction, the catalyst components and alcohol plus olefin are mixed and heated to the reaction temperature. The hydroperoxide is then metered in slowly. After completion of the reaction, the catalyst components can be filtered off and reused (the simplest case, i.e. when both are heterogeneous), or they must be removed from the product with water. The resultant xcex1-hydroxy ethers can generally be purified by distillation, but this is often unnecessary.
The amphiphilic compounds of the present invention are mostly superior by their extremely low critical micelle concentrations (CMC) and very low surface/interfacial tensions, e.g. in relation to: paraffin. These characteristics are due to the special structures of the compounds, namely at least two hydrophilic groups and at least two hydrophobic ones. Furthermore, most of said compounds have rather high hydrophilic suspending power and are exceptionally mild on the skin. Some of them are extremely rapid wetting agents.
The amphiphilic compounds of this invention are particularly useful as emulsifiers, demulsifiers, detergents, dispersants, and hydrotropes or cryptans (in the case of cyclic compounds) in industrial and domestic applications.
The instant invention furthermore relates to the use of the amphiphilic compounds in the areas of ore mining, metal working, surface finishing, plastics production and processing, cosmetics, medicine, food processing and preparation, and as auxiliaries for the application of crop protectants, and adjuvants in medical applications, as textile auxiliaries, as auxiliaries for the cleaning and washing of textiles, as auxiliaries for the cleaning of hard surfaces and as auxiliaries for the cleaning and washing of skin and hair.
Said compounds can be combined with any customary anionic, nonionic, cationic, and ampholytic surface-active substances. Examples of nonionic surface-active substances suitable for said combinations include fatty acid glycerides, fatty acid polyglycerides, fatty acid esters, ethoxylates of higher alcohols, polyoxyethylene fatty acid glycerides, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene castor oil or hardened castor oil derivatives, polyoxyethylene lanolin derivatives, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines, alkanol amines, alkylamine oxides, protein hydrolyzate derivatives, hydroxy mixed ethers, alkyl polyglycosides, and alkyl glucamides.
Examples of anionic surface-active substances useful for said combinations include soaps, ether carboxylic acids and salts thereof, alkyl sulfonates, xcex1-olefin sulfonates, sulfonates of higher fatty acid esters, higher alcohol sulfates, alcohol ether sulfates, hydroxy mixed ether sulfates, phosphate ester salts, taurides, isethionates, linear alkyl benzene sulfonates, alkylaryl sulfonates, polyoxyethylene fatty acid amide sulfates, and acylamino acid salts.
Examples of conventional cationic surface-active substances suitable for said combinations include alkyltrimethyl ammonium salts, dialkyldimethyl ammonium salts, alkyldimethylbenzyl ammonium salts, alkyl pyridinium salts, alkylisoquinolinium salts, benzethonium chlorides, and cationic acylamino acid derivatives.
Examples of ampholytic surface-active substances useful for said combinations include amino acids, betaines, sulfobetaines, imidazoline derivatives, soybean oil lipids, and lecithin.
Furthermore, the amphiphilic compounds of the present invention may also be combined with each other.
In addition, any commonly used additives may be added to the amphiphilic compounds of the invention. Such additives are specifically selected for a formulation and generally comprise inorganic salts, such as sodium chloride and sodium sulfate, builders, hydrotropes, such as cumene sulfonate, UV absorbers, fabric softeners, chelating agents, viscosity modifiers, fragrances etc.